FR2746307A1 - KERATINIC FIBER DYEING COMPOSITIONS CONTAINING PYRROLO-AZOLES; USE AS COUPLERS; DYEING PROCESS - Google Patents

Abstract

A composition for dyeing keratin fibres, particularly human hair, consisting of a medium suitable for use in dyeing and containing, as the coupler, at least one compound of formula (I) or (II), wherein R1 is particularly hydrogen, halogen, aryloxy, alkoxy, acyloxy, arylthio, alkylthio, heteroarylthio, heteroaryloxy, etc., each of R2 and R3, which are the same or different, is particularly hydrogen, halogen, alkyl, aryl, alkylthio, arylthio, benzylthio, etc., each of Za, Zb and Zc, which are the same or different, is a nitrogen atom or a carbon atom with a radical R4, R5, R6 or R7, each of R4, R6 and R7, which are the same or different, is particularly hydrogen, alkyl, aryl, a heterocyclic ring, halogen, etc., and R5 is particularly hydrogen, halogen, acyl, acyloxy, carbamoyl, etc., as well as at least one oxidation base, is disclosed.

Description

KERATIN FIBER DYEING COMPOSITIONS CONTAINING
PYRROLO-AZOLES; USE AS COUPLERS; PROCESS
DYEING.

The subject of the invention is a composition for dyeing keratin fibers, in particular human hair, containing at least one pyrroloazole compound as coupler and at least one oxidation base.

 It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, in particular ortho or paraphenylenediamines, ortho or paraamiphenols, heterocyclic compounds, generally called oxidation bases. The precursors of oxidation dyes, or oxidation base, are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored and coloring compounds.

We also know that we can vary the shades obtained with these oxidation bases by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as as indole compounds.

The variety of molecules involved in the oxidation bases and couplers, allows obtaining a rich palette of colors.

The so-called "permanent" coloration obtained thanks to these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be without drawbacks from the toxicological point of view, it must make it possible to obtain nuances in the desired intensity and present good resistance to external agents (light, bad weather, washing, permanent waving, perspiration, friction).

The dyes must also make it possible to cover white hair, and finally be the least selective possible, that is to say allow to obtain the smallest possible color differences throughout the same keratin fiber, which can be in fact differently sensitized (ie damaged) between its tip and its root.

However, the applicant has now discovered that it is possible to obtain new powerful dyes, not very selective and particularly resistant, capable of generating intense colorings in various shades, by using pyrrolo-azole compounds as couplers in the presence of an oxidation base.

This discovery is the basis of the present invention.

dans lesquelles:
R1 représente : un atome d'hydrogène ; un atome d'halogène tel que brome, chlore
ou fluor; un groupe acétylamido ; un radical alcoxy (tel que par exemple : méthoxy,
éthoxy, propyloxy, benzyloxy, méthoxyéthoxy, phénoxyéthoxy, 2-cyanoéthoxy,
phénéthyloxy, p-chlorobenzyloxy, méthoxyéthylcarbamoylméthoxy) ; un radical
aryloxy (tel que par exemple : phénoxy, 4-méthoxyphénoxy, 4-nitrophénoxy, 4
cyanophénoxy, 4-méthanesulfonamidophénoxy, 4-méthanesulfonylphénoxy, 3
méthylphénoxy, 1-naphtyloxy) ; un radical acyloxy (tel que par exemple : acétoxy,
propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, éthoxyalkyloxy, pymviloyloxy,
cinnamoyloxy, myristoyloxy) ; un radical arylthio (tel que par exemple : phénylthio, 4
carboxyphénylthio, 2-éthoxy 5-tert-butylphénylthio, 2-carboxyphénylthio, 4
méthanesulfonylphénylthio) ; un radical alkylthio (tel que par exemple : méthyfthio,
éthylthio, propylthio, butylthio, 2-cyanoéthylthio, benzylthio, phénéthylthio, 2
(diéthylamino)éthylthio, éthoxyéthylthio, phénoxyéthylthio) ; un radical hétéroarylthio
(tel que par exemple 5-phényl 2,3,4,5-tétrazolylthio, 2-benzothiazolylthio) ; un
radical hétéroaryloxy (tel que par exemple . 5-phényl 2,3,4,5-tétrazolyloxy, 2
benzothiazolyloxy) ; un radical thiocyano; un radical N,N-diéthyl thiocarbonylthio; un
radical dodécyl-oxythio carbonylthio ; un radical benzènesulfonamido ; un radical N
éthyltoluène sulfonamido ; un radical pentafluorobutanamido ; un radical 2,3,4,5, &
pentafluorobenzamido ; un radical p-cyanophényluréido, un radical N,N-diéthyl
sulfamoylamino; un radical pyrazolyle ; un radical imidazolyle ; un radical triazolyle
un radical tétrazolyle ; un radical benzimidazolyle ; un radical 1-benzyl Séthoxy 3
hydantoïnyle ; un radical 1-benzyl 3hydantoïnyle ; 5,5-diméthyl 2,4dioxo 3
oxazolidinyle ; un radical 2-oxy 1,2-dihydro 1-pyridinyle ; un alkylamido ; un
arylamido ; un radical NR'''Rv avec R"' et RN représentant, identiques ou différents,
un alkyle en C1-C4, un hydroxyalkyle; un carboxyle; un radical alcoxycarboxylique.The subject of the invention is a composition for dyeing keratin fibers and in particular human keratin fibers such as the hair, characterized in that it comprises, in a medium suitable for dyeing: - as a coupler, at minus a pyrrolo-azole compound corresponding to one of the following formulas (I) and (II), or one of its addition salts with an acid:

in which:
R1 represents: a hydrogen atom; a halogen atom such as bromine, chlorine
or fluorine; an acetylamido group; an alkoxy radical (such as for example: methoxy,
ethoxy, propyloxy, benzyloxy, methoxyethoxy, phenoxyethoxy, 2-cyanoethoxy,
phenethyloxy, p-chlorobenzyloxy, methoxyethylcarbamoylmethoxy); a radical
aryloxy (such as, for example: phenoxy, 4-methoxyphenoxy, 4-nitrophenoxy, 4
cyanophenoxy, 4-methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, 3
methylphenoxy, 1-naphthyloxy); an acyloxy radical (such as for example: acetoxy,
propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyalkyloxy, pymviloyloxy,
cinnamoyloxy, myristoyloxy); an arylthio radical (such as for example: phenylthio, 4
carboxyphenylthio, 2-ethoxy 5-tert-butylphenylthio, 2-carboxyphenylthio, 4
methanesulfonylphenylthio); an alkylthio radical (such as for example: methyfthio,
ethylthio, propylthio, butylthio, 2-cyanoethylthio, benzylthio, phenethylthio, 2
(diethylamino) ethylthio, ethoxyethylthio, phenoxyethylthio); a heteroarylthio radical
(such as for example 5-phenyl 2,3,4,5-tetrazolylthio, 2-benzothiazolylthio); a
heteroaryloxy radical (such as, for example. 5-phenyl 2,3,4,5-tetrazolyloxy, 2
benzothiazolyloxy); a thiocyano radical; an N, N-diethyl thiocarbonylthio radical; a
dodecyl-oxythio carbonylthio radical; a benzenesulfonamido radical; an N radical
ethyltoluene sulfonamido; a pentafluorobutanamido radical; a radical 2,3,4,5, &
pentafluorobenzamido; a p-cyanophenylureido radical, an N, N-diethyl radical
sulfamoylamino; a pyrazolyl radical; an imidazolyl radical; a triazolyl radical
a tetrazolyl radical; a benzimidazolyl radical; a 1-benzyl Sethoxy 3 radical
hydantoinyl; a 1-benzyl 3hydantoinyl radical; 5,5-dimethyl 2,4dioxo 3
oxazolidinyl; a 2-oxy 1,2-dihydro 1-pyridinyl radical; an alkylamido; a
arylamido; a radical NR '''Rv with R "' and RN representing, identical or different,
C1-C4 alkyl, hydroxyalkyl; a carboxyl; an alkoxycarboxylic radical.

R2 and R3, independently of one another, represent a hydrogen atom; a
halogen atom (such as bromine, chlorine or fluorine); a linear C1-CS alkyl radical
or branched, optionally substituted by one or two halogen, hydroxy,
alkoxy, aryloxy, amino, alkylamino, acyl, acylamino; a C1-C4 alkoxy radical; a
C1-C4 alkylthio radical; an arylthio radical; a benzylthio radical, an acyl radical
(such as acetyl; 3-phenyl propanoyl, benzoyl; 4-dodecyloxybenzoyl); a radical
acylamino; an acyloxy radical (such as acetoxy); a carbamoyl radical (such as
carbamoyl; N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dibutylcarbamoyl); NOT-
(2-dodecyl-oxyethyl) carbamoyl); a phenyl radical optionally substituted by
one or two halogen, nitro, sulfonyl, C1-C4 alkoxy, C1-C4 alkyl,
C1-C3 trifluoroalkyl, amino, alkylamino, an alkoxy carbonyl radical (such as
methoxycarbonyl, ethoxy-carbonyl, isopropyloxycarbonyl, tert-butyloxycarbonyl,
isobutyloxycarbonyl, butylcarbamoylethoxy-carbonyl, pertluorohexylethoxy-
carbonyl; an aryloxycarbonyl radical (such as phenoxycarbonyl, 2,5amyl
phenoxycarbonyl); a cyano radical; a nitro radical; a dialkylphosphono radical
(such as dimethylphosphono), a diarylphosphono radical (such as diphenyl
phosphono); a dialkoxyphospholyl radical (such as dimethoxyphospholyl); a
dialkylphosphinyl radical (such as dimethylphosphinyl); a diarylphos radical
phinyl (such as diphenylphosphinyl), an alkylsulfinyl radical (such as Sphenoxy-
propyl sulfinyl); an arylsulfinyl radical (such as 3-phenoxypropyl sulfinyl); a
arylsulfonyl radical (such as benzenesulfonyl, toluenesulfonyl); an alkyl radical
sulfonyl (methanesulfonyl, octanesulfonyl); a sulfonyloxy radical (such as
methanesulfonyloxy, toluenesulfonyloxy); an acylthio radical (such as acetylthio,
benzoylthio); a sulfamoyl radical (such as N-ethylsulfamoyl, N, N-diisoprnpyl-
sulfamoyl, N, N-diethyl-sulfamoyl); a thiocyanate radical; a thiocarbonyl radical
(such as methylthiocarbonyl, phenylthio carbonyl)
Za, Zb and Z, independently of one another, represent a nitrogen atom or a
carbon atom carrying a radical R4, R5, R6 or R7;
R4, R6 and R7, identical or different, represent a hydrogen atom; a
linear or branched Ct-C20 alkyl radical, optionally substituted with 1 or 2
radicals R chosen from the group consisting of halogen, nitro, cyano, hydroxy,
alkoxy, aryloxy, amino, alkylamino, acylamino, carbamoyl, sulfonamido, sulfamoyl,
imido, alkylthio, arylthio, aryl, alkoxycarbonyl, acyl; an aryl radical (such as
phenyl or naphthyl), optionally substituted by 1 or 2 radicals R such as
previously defined; a 5 or 6-membered heterocycle having at least one
nitrogen, oxygen or sulfur atom (such as pyridyl, quinolyl, pyrrolyl,
morpholyle, furanyl, tetrahydrofuranyl, pyrazolyle, triazolyle, tétrazolyle, thiazolyle,
oxazolyle, imidazolyle or thiadiazolyle), optionally substituted by 1 or 2 radicals
R as defined above;
when R4, R6 and R7 denote an alkyl radical, an aryl radical or a heterocyde to
5 or 6 links (defined above), it can be linked to the carbon atom of the nucleus
via an oxygen, nitrogen or sulfur atom (in this case, R4, R6 and
R7 become XR4, XR6 or XR7 with X = O, NH, S);
R4, R6 and R7 can also denote a halogen atom (such as bromine, chlorine or
fluorine); an acyl radical, a sulfonyl radical; a sulfinyl radical; a radical
phosphonyl, a carbamoyl radical; a sulfamoyl radical; a cyano radical; a
siloxy radical, an amino radical; an acylamino radical; an acyloxy radical; a radical
carbamoyloxy; a sulfonamide radical; an imide radical; a ureido radical; a
sulfamoylamino radical; an alkoxycarbonylamino radical; an aryloxy radical
carbonylamino; an alkoxycarbonyl radical; an aryloxycarbonyl radical; a radical
carboxyl;
R5 denotes hydrogen; halogen; an acyl radical; an acyloxy radical; a radical
carbamoyl; an alkoxycarbonyl radical; a cyano radical; a nitro radical; a
dialkylphosphono radical, a diarylphosphono radical; a dialkoxyphos radical
pholyle; a dialkyl-phosphinyl radical; a diarylphosphinyl radical; a radical
alkylsufinyl; an aryl-sulfinyl radical, an alkylsulphonyl radical; an aryl radical
sulfonyl; a sulfonyloxy radical; an acylthio radical; a sulfamoyl radical; a
thiocyanate radical; a thiocarbonyl radical; a halogenated aryloxy radical (such as
pentafluorophenyloxy); a halogenated alkylamino (such as N, N-di (trifluoro methyl
amino); halogenated alkylthio (such as difluoromethylthio); substituted or unsubstituted aryl
by electron-withdrawing groups (for example Cl, NO2, F); a heterocycle (such as 2-benzoxazolyle, 2-benzothiazolyle; pyrazolyle, 5-chloro 1-tetrazolyle, 1 -tetrazolyle, 1-pynrolyle); - And at least one oxidation base.

Among the radicals R1 of formulas (I) and (II), preferred are the radicals chosen from the group consisting of: a hydrogen atom; C1-C4 alkoxy; phenoxy; phenoxy substituted with a halogen atom, C1-C4 alkyl, carboxyl, trifluoromethyl group; an acyloxy radical; benzyloxy; C1-C4 alkylthio; phenylthio; phenylthio substituted with a halogen atom, C1-C4 alkyl, carboxyl, trifluoromethyl group; C1-C4 alkylamido; phenylamido; an NR '"RN radical with R and Rlv representing, identical or different, a C1-C4 alkyl, a C1-C4 hydroxyalkyl; a carboxyl; a C1-C4 alkoxycarboxylic radical.

Among the radicals R1 of the formulas (I) and (II) defined above, more particularly preferred are the radicals chosen from the group consisting of: hydrogen; chlorine or bromine; methoxy or ethoxy; phenyloxy; 4-methylphenyloxy; acyloxy; benzyloxy; methylthio or ethylthio; phenylthio; 4-methylphenylthio; 2-tertio butylphenylthio; acetamido; phenylacetamido; dimethylamino; diethylamino; ethylmethylamino; (p-hydroxyethyl) methylamino.

And even more particularly, the R1 radicals chosen from the group consisting of: hydrogen are preferred; chlorine; ethoxy; phenoxy; benzyloxy; acyloxy; acetamido; dimethylamino.

Among the radicals R2 and R3 of formulas (I) and (II), preferred are the radicals chosen from the group consisting of: acyl; acyloxy; carbamoyl; alkoxycarbonyl; aryloxycarbonyl; cyano; nitro; alkylsulfinyl; arylsulfinyl; alkylsulfonyl; arylsulfonyl; sulfamoyl; halogenated alkyl C1-C4 alkyl, hydrogen.

Among the radicals R2 and R3 of the formulas (I) and (II) defined above, more particularly preferred are the radicals chosen from the group consisting of: acyl (such as acetyl, ethylcarbonyl, phenylcarbonyl); alkoxycarbonyl (such as methoxy- or ethoxycarbonyl); nitro; cyano; arylsulfonyl (such as phenylsulfonyl); carbamoyl (such as carbamoyl, N-ethylcarbamoyl); halogenated alkyl (such as tnfluoromethyl); hydrogen; C1-C4 alkyl (such as methyl, ethyl).

And even more particularly, the R2 radicals chosen from the group consisting of: cyano are preferred; hydrogen; methyl; phenyl and the radicals R3 chosen from the group consisting of alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl are preferred; aryloxycarbonyl; hydrogen; methyl; cyano.

Among the radicals R4, R6 and R7 of formulas (I) and (II), preferred are the radicals chosen from the group consisting of: a linear or branched C1-C4 alkyl radical; aryl such as phenyl; phenyl substituted with a halogen, a methoxy radical, a nitro group, a cyano group, a trifluoromethyl group, an amino group; cyano; nitro; acylamino; arylamino; alkylthio such as methylthio, ethylthio; arylthio such as phenylthio; carbamoyl such as carbamoyl,
N-ethylcarbamoyl; sulfonyl such as methylsulfonyl; alkoxycarbonyl such as methoxycarbonyl, ethyloxycarbonyl; aryloxycarbonyl such as phenoxycarbonyl acyl such as acetyl, ethylcarbonyl; hydrogen.

And even more particularly, the radicals R4, R6 and R7 of the formulas (I) and (II) are preferred, chosen from the group consisting of hydrogen; C1-C4 alkyl, linear or branched (such as methyl, ethyl, isopropyl); aryl such as phenyl; phenyl substituted by a halogen, a methoxy radical, a nitro group, a cyano group, a trifluoromethyl group, an amino group.

Among the radicals R5 of formulas (I) and (II) defined above, more particularly preferred are the radicals chosen from the group consisting of: acyl (such as acetyl, benzoyl, ethylcarbonyl); alkoxycarbonyl (such as methoxy- or ethoxycarbonyl, isopropoxycarbonyl); aryloxycarbonyl such as phenoxycarbonyl; nitro; cyano; arylsulfonyl (such as phenylsulfonyl); halogenated alkyl (such as trifluoromethyl); hydrogen.

And even more particularly, the R5 radicals chosen from the group consisting of: cyano are preferred; alkoxycarbonyl (such as methoxy- or ethoxycarbonyl); aryloxycarbonyl such as phenoxycarbonyl; halogenated alkyl (such as trifluoromethyl); hydrogen.

(ii) les pyrrolo-[2,1-c]-1,2,4-triazoles de formule:

dans lesquelles R1, R2, R3 et R4 ont les mêmes significations indiquées ci-dessus;
Comme exemples de composés de formule (la), on peut citer en particulier ceux pour lesquels:
- R1 désigne hydrogène ou chlore;
- R2 et R3 désignent respectivement : cyano et cyano ; éthyloxycarbonyle et cyano
trifluorométhyle et cyano ; phénylsulfonyle et cyano ; trifluorométhyle et éthyloxy
carbonyle ; éthyloxycarbonyle et éthyloxycarbonyle ; méthyloxycarbonyle et méthyle
oxycarbonyle; hydrogène et hydrogène ou hydrogène et méthyle;
- R4 désigne méthyle, éthyle, isopropyle, phényle ou hydrogène.Among the preferred compounds of the invention corresponding to formula (I), mention may be made of those chosen from the group consisting of: (i) pyrrolo- [1,2-b] -1,2,4-triazoles of formula

(ii) pyrrolo- [2,1-c] -1,2,4-triazoles of formula:

in which R1, R2, R3 and R4 have the same meanings indicated above;
As examples of compounds of formula (la), mention may be made in particular of those for which:
- R1 denotes hydrogen or chlorine;
- R2 and R3 denote respectively: cyano and cyano; ethyloxycarbonyl and cyano
trifluoromethyl and cyano; phenylsulfonyl and cyano; trifluoromethyl and ethyloxy
carbonyl; ethyloxycarbonyl and ethyloxycarbonyl; methyloxycarbonyl and methyl
oxycarbonyl; hydrogen and hydrogen or hydrogen and methyl;
- R4 denotes methyl, ethyl, isopropyl, phenyl or hydrogen.

As examples of compounds of formula (Ib), mention may be made in particular of those for which
- R1 denotes hydrogen or chlorine;
- R2 and R3 denote simultaneously: cyano or hydrogen;
- R4 denotes methyl, ethyl, isopropyl, phenyl or hydrogen.

b) les pyrrolo-[2,1-c]-1,2,4-triazoles de formule:

c) les pyrrolo-[1, 2-c]-imidazoles de formule:

d) les pyrrolo-[1, 2-ej-tétrazoles de formule:

e) les pyrrolo-[1, 2-a]-pyrroles de formule:

f) les pyrrolo-[1, 2-al-imidazoles de formule:

g) les pyrrolo-[1, 2-c]-1,2,3-triazoles de formule:

dans lesquelles R4, R5, R6 et R7 ont les mêmes significations indiquées ci-dessus.Among the preferred compounds of the invention corresponding to formula (II), mention may be made of those chosen from the group consisting of: a) pyrrolo- [1, 2-b] -1, 2,4-triazoles of formula:

b) pyrrolo- [2,1-c] -1,2,4-triazoles of formula:

c) pyrrolo- [1, 2-c] -imidazoles of formula:

d) pyrrolo- [1, 2-ej-tetrazoles of formula:

e) pyrrolo- [1, 2-a] -pyrroles of formula:

f) pyrrolo- [1, 2-al-imidazoles of formula:

g) pyrrolo- [1, 2-c] -1,2,3-triazoles of formula:

in which R4, R5, R6 and R7 have the same meanings indicated above.

As examples of compounds of formula (III), mention may be made in particular of those for which:
- R1 denotes hydrogen or chlorine;
- R2 and R3 respectively denote - methoxycarbonyl and cyano; ethyloxycarbonyl
and cyano; cyano and methoxycarbonyl or ethoxycarbonyl; cyano and trifluoro
methyl; cyano and phenylsulfonyl; methyloxycarbonyl and methyloxycarbonyl
hydrogen and hydrogen; hydrogen and methyl; trifluoromethyl and cyano or
trifluoromethyl and methyloxycarbonyl;
- R4 denotes methyl, ethyl, isopropyl, phenyl or hydrogen.

As examples of compounds of formula (lob), mention may be made in particular of those for which:
- R1 denotes hydrogen or chlorine;
- R2 and R3 denote respectively: cyano and methoxycarbonyl; methoxycarbonyl
and cyano; methoxycarbonyl and methoxycarbonyl; hydrogen and hydrogen or
hydrogen and methyl;
- R4 denotes methyl, ethyl, isopropyl, phenyl or hydrogen.

As examples of compounds of formula (llc), mention may be made in particular of those for which:
- R1 denotes acetamido, chlorine or hydrogen;
- R2 and R3 denote respectively: methoxycarbonyl and cyano;
- R4 denotes hydrogen;
- R5 denotes cyano.

As examples of compounds of formula (lid), mention may be made in particular of those for which:
- R1 denotes hydrogen or chlorine;
- R2 and R3 denote respectively: cyano and methoxycarbonyl; cyano and cyano
methoxycarbonyl and cyano, methoxycarbonyl and methoxycarbonyl; hydrogen and
hydrogen or hydrogen and methyl.

As examples of compounds of formula (island), mention may be made in particular of those for which:
- R1 denotes hydrogen or chlorine;
- R2 and R3 denote respectively: cyano and methoxycarbonyl;
- R5 denotes trifluoromethyl;
- R6 denotes phenyl or methyl;
- R7 denotes methyl.

As examples of compounds of formula (lof), mention may be made in particular of those for which:
- R1 denotes hydrogen or chlorine;
- R2, R3, R6 and R7 respectively denote:
methoxycarbonyl / cyano / cyano / phenyl; cyano / methoxycarbonyl / cyano / phenyl
cyano / methoxycarbonyl / methoxycarbonyl / phenyl;
hydrogen / hydrogen / hydrogen / hydrogen; hydrogen / hydrogen / methyl / methyl.

As examples of compounds of formula (zig), mention may be made in particular of those for which:
- R1 denotes hydrogen or chlorine;
- R2 denotes cyano;
- R3 denotes methoxycarbonyl;
- R5 denotes cyano.

The addition salts with an acid of the compounds of the invention can be chosen in particular from hydrochlorides, hydrobromides, tartrates, tosylates, benzenesulfonates, sulfates, lactates and acetates.

The compounds of the present invention, their synthesis intermediates and their preparation methods are described in the following patent applications:
EP-A-557 851, EP-A-578 248, EP-A-518 238, EP-A-456 226, EP-A488 909, EP-A488 248 and in the following publications: DR Liljegren Ber. 1964, 3436; EJ Browne,
JCS, 1962, 5149; P. Magnus, JACS, 1990, 112, 2465; P. Magnus, JACS, 1987, 109 2711; Angew. Chem. 1960, 72, 956; Rec. Trav. Chim. 1961, 80, 1075.

The compound or compounds of formula (I) or (II) preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition and more particularly from 0.005 to 6% by weight.

The nature of the oxidation base or bases which can be used in the dye composition according to the invention is not critical. This or these oxidation bases are preferably chosen from paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and their addition salts with an acid.

dans laquelle:
R8 représente un atome d'hydrogène, un radical alkyle en C1-C4, monohydroxy-alkyle en
C1-C4, polyhydroxyalkyle en C2-C4 ou alcoxy(C1-C4) alkyle(C1-C4), Rg représente un atome d'hydrogène, un radical alkyle en C1-C4, monohydroxy-alkyle en
C1-C4 ou polyhydroxyalkyle en C2-C4, Rlo représente un atome d'hydrogène, un atome d'halogène tel qu'un atome de chlore, un radical alkyle en C1-C4, sulfo, carboxy, monohydroxyalkyle en C1-C4 OU hydroxyalcoxy en C1-C4,
R11 représente un atome d'hydrogène ou un radical alkyle en C1-C4. Among the paraphenylenediamines which can be used as oxidation bases in the dye composition according to the invention, mention may in particular be made of the compounds corresponding to the following formula (III), and their addition salts with an acid:

in which:
R8 represents a hydrogen atom, a C1-C4 alkyl radical, a monohydroxy-alkyl radical
C1-C4, C2-C4 polyhydroxyalkyl or (C1-C4) alkoxy (C1-C4) alkyl, Rg represents a hydrogen atom, a C1-C4 alkyl radical, monohydroxy-alkyl
C1-C4 or C2-C4 polyhydroxyalkyl, Rlo represents a hydrogen atom, a halogen atom such as a chlorine atom, a C1-C4 alkyl radical, sulfo, carboxy, C1-C4 monohydroxyalkyl OR hydroxyalkoxy in C1-C4,
R11 represents a hydrogen atom or a C1-C4 alkyl radical.

In formula (III) above, and when Rlo is different from a hydrogen atom, then
Ra and R9 preferably represent a hydrogen atom and R10 is preferably identical to R11, and when R10 represents a halogen atom, then R8, R9 and R10 preferably represent a hydrogen atom.

Among the paraphenylenediamines of formula (III) above, there may be mentioned more particularly paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-P-hydroxyethyl paraphenylenediamine, 2-p-hydrnxyethylethyloxy paraphenylenediamine, 6-dimethyl paraphenylene diamine, 2, Sdiethyl paraphenylenediamine, 2,3-dimethyl paraphenylene diamine, N, N-bis- (ss-hydroxyethyl) paraphenylenediamine, 4-amino 1- (ss-methoxyethyl) amino benzene, 2-chloro paraphenylenediamine, and their addition salts with an acid.

dans laquelle: Qt et Q2, identiques ou différents, représentent un radical hydroxyle ou NHR15 dans lequel R15 représente un atome d'hydrogène ou un radical alkyle en C1-C4,
R12 représente un atome d'hydrogène, un radical alkyle en C1-C4, monohydroxyalkyle en C,-C4, polyhydroxyalkyle en C2-C4 ou aminoalkyle en C1-C4 dont le reste amino peut être substitué, R13 et R14, identiques ou différents, représentent un atome d'hydrogène ou d'halogène ou un radical alkyle en C1-C4,
W représente un radical pris dans le groupe constitué par les radicaux suivants: -(CH2)n- ; (CH2)m-O-(CH2)m- ; -(CH2)m-CHOH-(CH2)m- et

dans lesquels n est un nombre entier compris entre 0 et 8 inclusivement et m est un nombre entier compris entre 0 et 4 inclusivement.Among the bisphenylalkylenediamines which can be used as oxidation bases in the dye composition according to the invention, mention may in particular be made of the compounds corresponding to the following formula (IV), and their addition salts with an acid:

in which: Qt and Q2, identical or different, represent a hydroxyl radical or NHR15 in which R15 represents a hydrogen atom or a C1-C4 alkyl radical,
R12 represents a hydrogen atom, a C1-C4 alkyl, C-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl or C1-C4 aminoalkyl in which the amino residue can be substituted, R13 and R14, identical or different, represent a hydrogen or halogen atom or a C1-C4 alkyl radical,
W represents a radical taken from the group consisting of the following radicals: - (CH2) n-; (CH2) mO- (CH2) m-; - (CH2) m-CHOH- (CH2) m- and

in which n is an integer between 0 and 8 inclusive and m is an integer between 0 and 4 inclusive.

Mention may more particularly be made, among the bis-phenylalkylenediamines of formulas (IV) above, of N, N'-bis- (p-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1, Sdiamino 2- propanol, N, N'-bis- (P-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N ' -bis- (p-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bîs- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N '-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, and their addition salts with an acid.

Among these bis-phenylalkylenediamines of formula (IV), N, N'-bis- (p-hydroxyethyl) N, N'bis- (4'-aminophenyl) 1,3-diamino propanol or one of its salts d addition with an acid are particularly preferred.

dans laquelle:
R16 représente un atome d'hydrogène, un radical alkyle en C1-C4, monohydroxyalkyle en C1-C4, alcoxy(C1-C4)alkyle(C1-C4) OU aminoalkyle en C1-C4,
R17 représente un atome d'hydrogène ou de fluor, un radical alkyle en C1-C4, monohydroxyalkyle en C1-C4, polyhydroxyalkyle en C2-C4, aminoalkyle en C1-C4, cyanoalkyle en C1-C4 ou alcoxy(C1-C4)alkyle(C1-C4), étant entendu qu'au moins un des radicaux R16 ou R17 représente un atome d'hydrogène.Among the para-aminophenols which can be used as oxidation bases in the dye composition according to the invention, mention may in particular be made of the compounds corresponding to the following formula (V), and their addition salts with an acid:

in which:
R16 represents a hydrogen atom, a C1-C4 alkyl radical, C1-C4 monohydroxyalkyl, (C1-C4) alkoxy (C1-C4) alkyl OR C1-C4 aminoalkyl,
R17 represents a hydrogen or fluorine atom, a C1-C4 alkyl, C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, C1-C4 aminoalkyl, C1-C4 cyanoalkyl or (C1-C4) alkoxy (C1-C4), it being understood that at least one of the radicals R16 or R17 represents a hydrogen atom.

Among the para-aminophenols of formula (V) above, mention may more particularly be made of para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4 amino 3-hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4amino 2- (p-hydroxyethyl aminomethyl) phenol, and their addition salts with an acid.

Among the ortho-aminophenols which can be used as oxidation bases in the dye composition according to the invention, there may be mentioned in particular 2-amino phenol, 2-amino 1-hydroxy 5-methyl benzene, 2-amino 1- hydroxy 6-methyl benzene, acetamido 2-amino phenol, and their acid addition salts.

Among the heterocyclic bases which can be used as oxidation bases in the dye composition according to the invention, mention may in particular be made of pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and their addition salts with an acid.

Among the pyridine derivatives, mention may more particularly be made of the compounds described for example in patents GB 1,026,978 and GB 1,153,196, such as 2,5 diaminopyridine, and their addition salts with an acid.

Among the pyrimidine derivatives, mention may be made more particularly of the compounds described, for example, in German patents DE 2,359,399 or Japanese patents JP 88-571 and
JP 91-333 495, such as 2,4,5,6-tetra-amino-pyrimidine, 4-hydroxy 2,5,6 triaminopyrimidine, and their addition salts with an acid.

Among the pyrazole derivatives, mention may more particularly be made of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications
WO 94/08969 and WO 94/08970 such as 4,5-diamino 1-met (p-hydroxyethyloxy) benzene, 2-amino 4- (p-hydroxyethylamino) 1-methoxy benzene, 1, 3-diamino benzene, 1,3-bis- (2,4-diaminophenoxy) propane, sesamol, anaphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 6hydroxy indoline, and their addition salts with an acid.

When present, these additional couplers preferably represent from 0.0005 to 5% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 3% by weight approximately of this weight.

The addition salts with an acid of the oxidation base (s) and / or additional couplers which can be used in the dye composition of the invention are in particular chosen from hydrochlorides, hydrobromides, sulphates and tartrates, lactates and acetates.

The medium suitable for dyeing (or support) generally consists of water or a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. As organic solvent, mention may, for example, be made of lower C1-C4 alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous products and mixtures thereof.

The solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

The pH of the dye composition according to the invention is generally between 3 and 12. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers.

Among the acidifying agents, there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid, sulfonic acids.

dans laquelle R est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en C1-C4 ; R18, R19, R20 et R21, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C1-C4 OU hydroxyalkyle en C1 C4. Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (VI) below:

in which R is a propylene residue optionally substituted by a hydroxyl group or a C1-C4 alkyl radical; R18, R19, R20 and R21, identical or different, represent a hydrogen atom, a C1-C4 alkyl radical OR C1-C4 hydroxyalkyl.

The dye composition according to the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic polymers , nonionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example silicones, film-forming agents, preserving agents, opacifying agents.

Of course, those skilled in the art will take care to choose the optional compound (s) mentioned above, in such a way that the advantageous properties intrinsically attached to the dye composition according to the invention are not, or not substantially, altered. by the addition (s) envisaged.

The dye composition according to the invention can be in lively forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.

A subject of the invention is also the use of the compounds of formula (I) or (II) above, as coupler, in combination with at least one oxidation base for the oxidation dyeing of keratin fibers and in particular of human keratin fibers such as hair.

Another object of the invention is a process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, using the dye composition as defined above.

According to this process, at least one dye composition as defined above is applied to the fibers, the color being revealed at acidic, neutral or alkaline pH using an oxidizing agent which is added just at the time of use. the dye composition or which is present in an oxidizing composition applied simultaneously or sequentially separately.

According to a particularly preferred embodiment of the dyeing process according to the invention, the dye composition described above is mixed at the time of use with an oxidizing composition containing, in a medium suitable for dyeing, minus an oxidizing agent present in an amount sufficient to develop coloring. The mixture obtained is then applied to the keratin fibers and left to stand for 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which it is rinsed, washed with shampoo, rinsed again and dried.

The oxidizing agent present in the oxidizing composition as defined above can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibers, and among which mention may be made of hydrogen peroxide, peroxide of urea, alkali metal bromates, persalts such as perborates and persulfates. Hydrogen peroxide is particularly preferred.

The pH of the oxidizing composition containing the oxidizing agent as defined above is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 approximately and even more preferably between 5 and 11. It is adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above.

The oxidizing composition as defined above may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.

The composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair. .

Another object of the invention is a device with several compartments or "kit" for dyeing or any other packaging system with several compartments, a first compartment of which contains the dye composition as defined above and a second compartment of which contains the oxidizing composition. as defined above.

These devices can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant.

Claims (36)

1. Composition for dyeing keratin fibers and in particular human keratin fibers such as the hair, characterized in that it comprises, in a medium suitable for dyeing: - as coupler, at least one pyrrolo- compound azole or one of its addition salts with an acid corresponding to one of the following formulas:

 in which:  R1 represents: a hydrogen atom; a halogen atom; an acetyl radical  amido; an alkoxy radical; an aryloxy radical; an acyloxy radical; an arylthio radical;  an alkylthio radical; a heteroarylthio radical; a heteroaryloxy radical; a radical  thiocyano; an N, N-diethyl thiocarbonylthio radical; a dodecyloxythio radical  carbonylthio; a benzene-sulfonamido radical an N-ethyltoluene radical  sulfonamido; a penta-fluorobutanamido radical; a radical 2,3,4,5, Spentafluoro-  benzamido; a p-cyano-phenylureido radical, an N, N-diethyl-sulfamoylamino radical;  a pyrazolyl radical; an imidazolyl radical; a triazolyl radical; a radical  tetrazolyl; a benzimidazolyl radical; a 1-benzyl 5-ethoxy 3-hydantoinyl radical;  a 1-benzyl 3-hydantoinyl radical; 5,5-dimethyl 2,4-dioxo 3-oxazolidinyl; a radical  2-oxy 1,2-dihydro 1-pyndinyl, an alkylamido; an arylamido; acetylamido; a radical  NR "'R"' with R "'and R representing, identical or different, a C1-C4 alkyl, a  hydroxyalkyl; a carboxyl; an alkoxycarboxylic radical;  R2 and R3, independently of one another, represent a hydrogen atom; a  halogen atom; a linear or branched C1-C5 alkyl radical, optionally  substituted by one or two halogen, hydroxy, alkoxy, aryloxy, amino,  alkylamino, acyl, acylamino; a C1-C4 alkoxy radical; a C1 alkylthio radical  C4; an arylthio radical; a benzylthio radical, an acyl radical; an acylamino radical;  an acyloxy radical; a carbamoyl radical; a phenyl radical optionally  substituted by one or two halogen, nitro, sulfonyl, C1-C4 alkoxy, alkyl  C1-C4, C1-C3 trifluoroalkyl, amino, alkylamino; an alkoxycarbonyl radical; a  aryloxycarbonyl radical, a cyano radical; a nitro radical; a dialkyl radical  phosphono; a diarylphosphono radical; a dialkoxyphospholyl radical; a radical  dialkylphosphinyl; a diarylphosphinyl radical; an alkylsulfinyl radical; a radical  arylsulfinyl; an arylsulfonyl radical; an alkylsulfonyl radical; a sulfonyS radical  oxy; an acylthio radical; a sulfamoyl radical; a thiocyanate radical; a radical  thiocarbonyl;  Za, Zb and Z, independently of one another, represent a nitrogen atom or a  carbon atom carrying a radical R4, R5, R6 or R7;  R4, R6 and R7, identical or different, represent a hydrogen atom; a  linear or branched C1-C20 alkyl radical, optionally substituted with 1 or 2  radicals R chosen from the group consisting of halogen, nitro, cyano, hydroxy,  alkoxy, aryloxy, amino, alkylamino, acylamino, carbamoyl, sulfonamido, sulfamoyl,  imido, alkylthio, arylthio, aryl, alkoxycarbonyl, acyl an aryl radical  optionally substituted with 1 or 2 radicals R as defined above; a  5 or 6-membered heterocycle having at least one nitrogen, oxygen or  sulfur optionally substituted by 1 or 2 radicals R as defined  previously;  when R4, R6 and R7 denote an alkyl radical, an aryl radical or a heterocyde to  5 or 6 links (defined above), it can be linked to the carbon atom of the nucleus  via an oxygen, nitrogen or sulfur atom (in this case, R4, R6 and  R7 become XR4, XR6 or XR7 with X = O, NH, S);  R4, R6 and R7 can also denote a halogen atom; an acyl radical; a  sulfonyl radical; a sulfinyl radical, a phosphonyl radical, a radical  arbamoyl; a sulfamoyl radical; a cyano radical; a siloxy radical, a radical  amino; an acylamino radical; an acyloxy radical; a carbamoyloxy radical; a  sulfonamide radical; an imide radical; a ureido radical; a sulfamoylamino radical;  an alkoxycarbonylamino radical; an aryloxycarbonylamino radical; an alkoxy radical  carbonyl; an aryloxycarbonyl radical; a carboxyl radical;  R5 denotes hydrogen; halogen; an acyl radical; an acyloxy radical; a radical  carbamoyl; an alkoxycarbonyl radical; a cyano radical; a nitro radical; a  dialkylphosphono radical; a diarylphosphono radical; a dialkoxy radical  phospholyl; a dialkylphosphinyl radical; a diarylphosphinyl radical; a radical  alkylsufinyl; an arylsulfinyl radical; an alkylsulfonyl radical; a radical  arylsulfonyl; a sulfonyloxy radical, an acylthio radical; a sulfamoyl radical; a  thiocyanate radical; a thiocarbonyl radical; a halogenated aryloxy radical; a radical  halogenated alkylamino; halogenated alkylthio; an aryl substituted or not by  electron-withdrawing groups; a heterocycle; - And at least one oxidation base. 2. Composition according to Claim 1, characterized in that the radicals R1 of the formulas (I) and (II) are chosen from the group consisting of: a hydrogen atom; C1-C4 alkoxy, phenoxy; phenoxy substituted with a halogen atom, C1-C4 alkyl, carboxyl, trifluoromethyl group; an acyloxy radical; benzyloxy; C1-C4 alkylthio; phenylthio; phenylthio substituted with a halogen atom, C1-C4 alkyl, carboxyl, trifluoromethyl group; C1-C4 alkylamido; phenylamido; a radical NR "'RN with R"' and RN representing, identical or different, a C1-C4 alkyl, a hydroxy-C1-C4 alkyl; a carboxyl; a C1-C4 alkoxycarboxylic radical. 3. Composition according to Claim 2, characterized in that the radicals R1 of the formulas (I) and (II) are chosen from the group consisting of: hydrogen; chlorine or bromine; methoxy or ethoxy; phenyloxy; 4-methylphenyloxy; acyloxy; benzyloxy; methylthio or ethylthio; phenylthio; 4-methylphenylthio; 2-tertio butylphenylthio; acetamido; phenylacetamido; dimethylamino; diethylamino; ethylmethylamino; (p-hydroxyethyl) methylamino. 4. Composition according to claim 2 or 3, characterized in that the radicals R1 of formulas (I) and (II) are chosen from the group consisting of: hydrogen; chlorine; ethoxy; phenoxy; benzyloxy; acyloxy; acetamido; dimethylamino. 5. Composition according to any one of claims 1 to 4, characterized in that the radicals R2 and R3 of formulas (I) and (II) are chosen from the group consisting of: acyl; acyloxy; carbamoyl; alkoxycarbonyl; aryloxycarbonyl; cyano; nitro; alkylsulfinyl; arylsulfinyl; alkylsulfonyl; arylsulfonyl; sulfamoyl; halogenated alkyl C1-C4 alkyl, hydrogen. 6. Composition according to claim 5, characterized in that the radicals R2 and R3 of formulas (I) and (II) are chosen from the group consisting of: acyl; alkoxycarbonyl; nitro; cyano; arylsulfonyl; carbamoyl; halogenated hydrogen; C1-C4 alkyl 7. Composition according to claim 5 or 6, characterized in that the radicals R2 of formulas (I) and (II) are chosen from the group consisting of: cyano; methyl hydrogen; phenyl and that the radicals R3 of formulas (I) and (II) are chosen from the group consisting of: alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl aryloxycarbonyl; hydrogen; methyl; cyano. 8. Composition according to any one of claims 1 to 7, characterized in that the radicals R4, R6 and R7 of formulas (I) and (II) are chosen from the group consisting of: a C1-C4 alkyl radical , linear or branched; aryl; phenyl substituted by a halogen, a methoxy radical, a nitro group, a cyano group, a trifluoromethyl group, an amino group; cyano; nitro; acylamino, arylamino; alkylthio; arylthio; carbamoyl sulfonyl; alkoxycarbonyl; aryloxycarbonyl; acyl, hydrogen. 9. Composition according to Claim 8, characterized in that the radicals R4, R6 and R7 of the formulas (I) and (II) are chosen from the group consisting of: hydrogen; C1-C4 alkyl, linear or branched; aryl; phenyl substituted by a halogen, a methoxy radical, a nitro group, a cyano group, a trifluoro methyl group, an amino group. 10. Composition according to any one of claims 1 to 9, characterized in that the radicals R5 of formulas (I) and (II) are chosen from the group consisting of: acyl; alkoxycarbonyl; aryloxycarbonyl; nitro; cyano; arylsulfonyl; halogenated alkyl; hydrogen 11. Composition according to any one of claims 1 to 10, characterized in that the radicals R5 are chosen from the group consisting of: cyanoalkoxycarbonyl; aryloxycarbonyl; halogenated alkyl; hydrogen. 12. Composition according to any one of claims 1 to 11, characterized in that the compounds of formula (I) are chosen from the group consisting of: (i) pvrrolo-Fî .2-bl-1 2,4 -triazoles of formula:

 (ii) pyrrolo- [2,1-c] -1,2,4-triazoles of formula:

 in which R1, R2, R3 and R4 have the same meanings indicated in any one of claims 1 to 11. 13. Composition according to Claim 12, characterized in that the compounds of formula (la) are those for which:  - R1 denotes hydrogen or chlorine,  - R2 and R3 respectively denote cyano and cyano; ethoxycarbonyl and cyano  trifluoromethyl and cyano; phenylsulfonyl and cyano; trifluoromethyl and ethyloxy  carbonyl; ethoxycarbonyl and ethoxycarbonyl; methoxycarbonyl and meth  oxycarbonyl; hydrogen and hydrogen or hydrogen and methyl;  - R4 denotes methyl, ethyl, isopropyl, phenyl or hydrogen.  - R4 denotes methyl, ethyl, isopropyl, phenyl or hydrogen.  - R2 and R3 denote simultaneously: cyano or hydrogen;  - R1 denotes hydrogen or chlorine; 14 Composition according to Claim 12, characterized in that the compounds of formula (lb) are those for which 15. Composition according to any one of claims 1 to 11, characterized in that the compounds of fonmule (ll) are chosen from the group consisting of: a) pyrrolo-1, 2-bj-1, 2,4 -triazoles of formula:

 b) pyrrolo- [2,1-c] -1,2,4-triazoles of formula:

 c) pyrrolo- [1, 2-c] -imidazoles of formula:

  d) pyrrolo- [1, 2-e] -tetrazoles of formula:

 e) the ovrrolo- [1,2-a] -pyrroles of formula:

 f) pyrrolo- [1,2-al-imidazoles of formula:

 o) the ovrrolo- [1. 2-cl-1.2.3-triazoles of formula:

 in which R1, R2, R3, R4, R, R8 and R7 have the same meanings indicated in any one of claims 1 to 10. 16. Composition according to Claim 15, characterized in that the compounds of formula (IIa) are those for which:  - R1 denotes hydrogen or chlorine;  - R2 and R3 denote respectively: methoxycarbonyl and cyano; ethoxycarbonyl and  cyano; cyano and methoxycarbonyl or ethoxycarbonyl; cyano and trifluoromethyl  cyano and phenylsulfonyl; methoxycarbonyl and methoxy-carbonyl; hydrogen and  hydrogen; hydrogen and methyl; trifluoromethyl and cyano or trifluoromethyl and  methoxycarbonyl;  - R4 denotes methyl, ethyl, isopropyl, phenyl or hydrogen. 17. Composition according to Claim 15, characterized in that the compounds of formula (IIb) are those for which:  - R1 denotes hydrogen or chlorine;  - R2 and R3 denote respectively: cyano and methoxycarbonyl; methoxycarbonyl  and cyano; methoxycarbonyl and methoxycarbonyl; hydrogen and hydrogen  hydrogen and methyl;  - R4 denotes methyl, ethyl, isopropyl, phenyl or hydrogen. 18. Composition according to Claim 15, characterized in that the compounds of formula (llc) are those for which  - R1 denotes acetamido, hydrogen or chlorine;  - R2 and R3 denote respectively: methoxycarbonyl and cyano;  - R4 denotes hydrogen;  - R5 denotes cyano. 19. Composition according to Claim 15, characterized in that the compounds of formula (lid) are those for which:  - R1 denotes hydrogen or chlorine;  - R2 and R3 denote respectively: cyano and methoxycarbonyl; cyano and cyano  methoxycarbonyl and cyano; methoxycarbonyl and methoxycarbonyl; hydrogen and  hydrogen; hydrogen and methyl. 20. Composition according to Claim 15, characterized in that the compounds of formula (island) are those for which:  - R1 denotes hydrogen or chlorine;  - R2 and R3 denote respectively: cyano and methoxycarbonyl;  - R5 denotes trifluoromethyl;  - R6 denotes phenyl or methyl;  - R7 denotes methyl. 21. Composition according to Claim 15, characterized in that the compounds of formula (lof) are those for which  - R1 denotes hydrogen or chlorine;  - R2, R3, R6 and R7 respectively denote:  methoxycarbonyl / cyano / cyano / phenyl; cyano / methoxycarbonyl / cyano / phenyl cyano / methoxycarbonyl / methoxycarbonyl / phenyl; Hydrogen Hydrogen  hydrogen / hydrogen; hydrogen / hydrogen / methyl / methyl. 22. Composition according to Claim 15, characterized in that the compounds of formula (IIg) are those for which:  - R1 denotes hydrogen or chlorine;  - R2 denotes cyano;  - R3 denotes methoxycarbonyl;  - Rs denotes cyano. 23. Composition according to any one of the preceding claims, characterized in that the addition salts with an acid of the compounds of formula (I) or (II) are chosen from hydrochlorides, hydrobromides, tartrates, tosylates, benzenesulfonates, sulfates, lactates and acetates. 24. Composition according to any one of the preceding claims, characterized in that the compound or compounds of formula (I) or (II) represent from 0.0005 to 12% by weight of the total weight of the dye composition. 25. Composition according to Claim 24, characterized in that the compound or compounds of formula (I) or (II) represent from 0.0005 to 6% by weight of the total weight of the dye composition. 26. Composition according to any one of the preceding claims, characterized in that the oxidation base or bases are chosen from paraphenylene diamines, bis-phenylalkylenediamines, paraaminophenols, ortho-aminophenols, heterocyclic bases, and their addition salts with an acid. 27. Composition according to any one of the preceding claims, characterized in that the oxidation base or bases represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition. 28. Composition according to Claim 27, characterized in that the oxidation base or bases represent from 0.005 to 6% by weight approximately of the total weight of the dye composition. 29. Composition according to any one of the preceding claims, characterized in that it also contains one or more additional couplers different from the compounds of formula (I) or (II) and / or one or more direct dyes. 30. Composition according to any one of the preceding claims, characterized in that the medium suitable for dyeing (or support) consists of water or of a mixture of water and at least one chosen organic solvent among C1-C4 lower alkanols, glycerol, glycols and glycol ethers, aromatic alcohols, analogues and their mixtures. 31. Composition according to any one of the preceding claims, characterized in that it has a pH of between 3 and 12. 32. Composition according to any one of the preceding claims, characterized in that it is in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular hair. humans. 33. Use of the compounds of formula (I) or (II) or of their addition salts with an acid as defined in any one of claims 1 to 23, as couplers in compositions for dyeing oxidation of keratin fibers and in particular human keratin fibers such as the hair, in combination with at least one oxidation base. 34. Process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that at least one dye composition as defined in any one of claims 1 is applied to these fibers at 32, the color being revealed at acid, neutral or alkaline pH using an oxidizing agent which is added just at the time of use to the dye composition or which is present in an oxidizing composition applied simultaneously or sequentially with separately. 35. Method according to claim 34, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates. 36. Device with several compartments, or dye "kit" with several compartments, a first compartment of which contains a dye composition as defined in any one of claims 1 to 32 and a second compartment of which contains an oxidizing composition.